Catalyst for the Treatment of Organic Compounds

ABSTRACT

A catalyst for the hydroprocessing of organic compounds, composed of an interstitial metal hydride having a reaction surface at which monatomic hydrogen is available. The activity of the catalyst is maximized by avoiding surface oxide formation. Transition metals and lanthanide metals compose the compound from which the interstitial metal hydride is formed. The catalyst&#39;s capabilities can be further enhanced using radio frequency (RF) or microwave energy.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a catalyst for the hydroprocessing of organiccompounds. Hydroprocessing includes all types of petroleum hydrocrackingand hydrotreating processes. This catalyst can be used for the lowpressure hydrogenation of organic compounds and petroleum usingconventional heat sources. This catalyst's capabilities can be furtherenhanced using radio frequency (RF) or microwave energy.

2. Description of Related Art

Hydrocarbons are subjected to a variety of physical and chemicalprocesses to produce higher value products. These processes includefractionation, isomerization, bond dissociation and reformation,purification, and increasing hydrogen content. The processes tend torequire high pressures and temperatures. Catalysts are employed in theprocesses for various reasons including, but not limited to, reducingthe temperatures and pressures at which the hydrocarbon conversionreaction takes place. The term “hydroprocessing” is used to refer to theencompassing superset of these processes in which hydrogen is used.

Petroleum or crude oil is a naturally occurring mixture of hydrocarbonsand smaller amounts of organic compounds containing heteroatoms such assulfur, oxygen, nitrogen, and metals (mostly nickel and vanadium). Thepetroleum products obtained from crude oil processing vary considerably,depending on market demand, crude oil quality, and refinery objectives.In current industrial practices, crude oils are submitted todistillation under atmospheric pressure and under vacuum. Thedistillation fractions (including the residual fractions) undergofurther catalytic refining processes so high-value products can beproduced.

The hydrogen content of petroleum products is an important index oftheir economic value. In conventional hydrocracking and hydrotreatingprocesses, the hydrogenation reactions of aromatic compounds play acrucial role. Heavy residual compounds are normally aromatic in nature.The complete or partial saturation of these compounds by hydrogenaddition is an important step in their cracking into smaller, morevaluable compounds. Conventional heavy oil hydrocracking processesrequire relatively high temperature (e.g. greater than 400° C.) and veryhigh pressure (e.g. greater than 1000 psi). In current hydrotreating andhydroreforming processes, supported Ni—Mo and Co—Mo sulfided catalystsbecome active only at the high temperature range. In order for reactionsto take place at a favorable lower temperature range, expensive noblemetal catalysts are usually used in order to achieve good hydrogenationefficiency. Attempts have been made to find new classes of catalyststhat would significantly lower the process parameters, while increasingthe hydrogenation efficiency in terms of deep reduction of aromaticcontent, but the progress made thus far is mostly small improvementsover existing catalyst systems.

As the name implies, hydrocracking combines catalytic cracking andhydrogenation by means of a bifunctional catalyst to accomplish a numberof favorable transformations of particular value for the selectedfeedstocks. In a typical bifunctional catalyst, the cracking function isprovided by an acidic support, whereas the hydrogenation function isprovided by noble metals, or non-noble metal sulfides from PeriodicTable Groups 6, 9, and 10 (based on the 1990 IUPAC system in which thecolumns are assigned the numbers 1 to 18). Hydrocracking is a versatileprocess for converting a variety of feedstocks, ranging from naphthasthrough heavy gas oils, into useful products. Its most uniquecharacteristic involves the hydrogenation and breakup of polynucleararomatics. Significant portions of these feedstocks are convertedthrough hydrocracking into smaller-sized and more useful productconstituents. However, some of the large aromatic complexes within thesefeedstocks, once partially hydrogenated via hydrocracking, can proceedto dehydrogenate forming coke on the catalysts. Coke formation is one ofmany deactivation mechanisms that reduce catalyst life.

In many refineries, the hydrocracker serves as the major supplier of jetand diesel fuel components (middle distillates). Because of the highpressure required and hydrogen consumption, conventional hydrocrackersare very costly to build and to operate. By developing a class ofcatalysts with high selectivity for middle distillates and favorableoperating conditions, it is possible to significantly reduce these highcosts while maximizing the production of the middle distillates.

To remove undesirable heteroatoms, desulfurization, denitrogenation, anddemetallization processes are also accomplished using hydroprocessingmethods. Because the values of petroleum products are directly relatedto their hydrogen contents, the effective hydrogenation of products ishighly desirable in all stages of petroleum refining.

Metals, such as platinum, deposited on oxide supports, such as aluminaor silica, are widely used in catalysts for hydrocarbon reformingreactions. The deposited metal provides reactive sites at which thedesired reactions can occur. However, catalysts using these metals havethe problem of being rendered inactive if heavy polyaromatic organiccompounds build up and occupy or block the sites. The removal of sulfurand sulfur compounds are also a problem for these catalysts. Sulfurreacts with the catalytic sites of Pt or Pd metals and can alsodeactivate these sites by chemically binding to the metals. Successfulcatalysis requires that a suitable high local concentration of hydrogenbe maintained during the catalytic process. Pressure and temperatureconditions are selected to favor formation of the desired product, toprovide a suitable rate of conversion, and to avoid rapid deactivationof the catalytic surface.

Hydroprocessing catalysts and their respective components can take manyforms and structures. Much is known about optimizing catalystperformance for specific processes (e.g., hydrogenation, hydrocracking,hydrodemetallization and hydrodesulfurization). Regarding the catalystform, the catalyst can be used as a powder, extrudate, or preformedmatrix based upon the type of chemical reactor design selected (e.g.,fluidized bed, fixed bed, catalytic converter).

An overall need remains, however, for improved catalysts and catalytichydroprocesses that can be carried out under relatively mild conditions.

SUMMARY OF THE INVENTION

In one aspect, the invention provides a catalyst that includes aninterstitial metal hydride having a reaction surface and monatomichydrogen at the reaction surface. The reaction surface may besubstantially free of an oxide layer.

In another aspect, the invention provides a catalyst having a support,an RF or microwave energy absorber and a catalytically active phase. Thecatalytically active phase stores and produces hydrogen in monatomicform. The RF or microwave energy absorber may be the catalyticallyactive phase.

In a further aspect, the invention provides a catalyst including a metalhydride having a reaction surface and monatomic hydrogen at the reactionsurface. The catalyst also includes at least one of a hydroprocessingcomponent, a cracking component and combinations thereof.

In another aspect, the invention provides a mixture comprising aninterstitial metal hydride and a liquid organic compound.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagram of a process for the production of a first catalystof the present invention;

FIG. 2 is a diagram of a process for the production of a second catalystof the present invention;

FIG. 3 is a diagram of a process for the production of a third catalystof the present invention;

FIG. 4 is a diagram of a process for the production of a fourth catalystof the present invention;

FIG. 5 is a schematic diagram of a reactor configuration for the processof the present invention;

FIG. 6 is a schematic diagram of a reactor configuration for the processof the present invention with the capability of preheating the gas andliquid and recirculating the reaction mixture or components of thereaction mixture internally and externally;

FIG. 7 is a schematic diagram of a reactor configuration for the processof the present invention having the capability of recirculating thecatalyst for regeneration or recharging;

FIG. 8 is a schematic diagram for improved handling the output for anyreactor design for the process of the present invention having thecapability of separating product into gas and liquid;

FIG. 9 is a schematic representation for improved handling the outputfor any reactor design for the process of the present invention havingthe capability of gas product collection, gas product recycling, liquidproduct collection and liquid product recycling and a means forinjecting the gas and liquid to be recycled to be injected back into thefeed or input stream.

FIG. 10 is a plot of hydrogen pressure versus hydrogen content atvarious temperatures for a catalyst of the present invention;

FIG. 11 is a plot of total hydrogen versus temperatures at ambientpressure for three catalysts of the present invention;

FIG. 12 is a plot of dielectric loss tangent against microwave frequencyfor pitch residuum and microwave processed pitch;

FIG. 13 is a graph of pressure, temperature, microwave power andhydrogen flow as a function of time for a reaction catalyzed by the iMeHCat 300 with palladium coated USY support.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed to catalysts containing interstitialmetal hydrides, having reaction surfaces at which monatomic hydrogen isavailable, and to any catalytic processes making use of these materials.The interstitial metal hydrides of the present invention (nowspecifically being defined as iMeH) are composed of alloyed metalscombined with atomic hydrogen that is stored interstitially within theirmetal alloy matrix. These interstitial metal hydrides (iMeH), whenconfigured according to the present invention comprise a catalystcapable of absorbing molecular hydrogen, and reacting monatomic hydrogenat the reaction surface. The catalysts of the present invention havereaction surfaces that may be kept substantially free of an oxide layer.Undesirable oxide species can inhibit the monatomic hydrogen fromparticipating in the catalytic process. Production of an oxide layer isavoided, and reaction surfaces are kept substantially free of an oxidelayer, by minimizing exposure of the catalyst to oxygen or water vaporat elevated temperatures, such as temperatures above 30° C. Exposure tooxygen and water vapor is minimized by surrounding the catalyst with ablanketing atmosphere of an inert gas such as nitrogen or argon whichhas been exposed to a desiccant. It has been found that the monatomichydrogen concentration at the catalyst surface is maximized by exclusionof oxygen and water vapor at elevated temperatures. Monatomic hydrogenat the iMeH catalyst surface is monatomic hydrogen in close enoughproximity to the surface to react, in the monatomic form, with afeedstock in contact with the surface.

In use, the interstitial metal hydride can be directly combined with thefeedstock, at reaction temperatures, or the iMeH may be first formedinto a composite with other materials to further enhance catalyticactivity. The catalytic process of the present invention includescontacting the feedstock with a catalyst comprising an interstitialmetal hydride, having a reaction surface, to produce acatalyst-feedstock mixture, applying energy to at least one of thecatalyst and the catalyst-feedstock mixture, producing monatomichydrogen at the reaction surface of the interstitial metal hydride, andreacting the feedstock with the monatomic hydrogen. In one embodiment ofthe invention, the feedstock is an organic compound.

Again, the interstitial metal hydrides are composed of alloyed metalscombined with atomic hydrogen, which is stored interstitially within themetal alloy matrix. This matrix can have a crystalline or amorphousstructure. The iMeH is especially suited to accommodating atomichydrogen, abstracted from molecular hydrogen. The quantity of atomichydrogen in the interstitial metallic hydrides has a measurable value,which is a function of alloy composition, and operating temperature andpressure. The hydrogen stored within an iMeH is not subject to ionic orcovalent bonding. In an iMeH, the ratio of hydrogen to metal atoms mayvary over a range and may not be expressible as a ratio of small wholenumbers. The iMeH compounds of the present invention are able todissociate diatomic hydrogen molecules at the surface into monatomichydrogen, absorb copious amounts of monatomic hydrogen thus produced,and desorb the monatoinic hydrogen under the appropriate conditions. Aheat of absorption is produced when the molecular hydrogen dissociatesinto atomic hydrogen and the hydrogen atoms position themselvesinterstitially in the structure of the material. Additional energy at asuitable steady state process temperature and pressure is required forthe release of monatomic hydrogen from within the catalyst. This energycan be derived from the process heat of reaction or from externalapplication of energy or both. The atomic hydrogen thus provided isavailable to promote hydroprocessing and hydrogenation reactions.Without intending to be limited by the theory, the catalyst's activityof the present invention is believed to be due to the high concentrationof available monatomic hydrogen, which the iMeH uniquely provide by thenature of their dissociation and absorption of molecular hydrogen (H₂)and subsequent reaction exchange of highly reactive monatomic hydrogen(H•) at the surface.

The catalytic activity of the catalyst of the present invention can beenhanced and controlled by exposing the catalyst to RF or microwaveenergy (1000 m−10⁻⁴ m wavelength), either in the absence or presence offuel fired heating or resistive heating. The RF or microwave energy canprovide for a significant increase in hydroprocessing efficiency incomparison to conventional heating. Furthermore the microwave energy canbe modulated and controlled in such a manner as to optimize the reactionexchange of the monatomic hydrogen from the iMeH. In one embodiment ofthe invention, the iMeH catalyst component is placed in contact with aseparate absorber of RF or microwave energy. The separate absorber of RFor microwave energy absorbs the energy and transfers it to the iMeHthrough thermal conduction or convection, and may be one or morecompounds such as silicon carbide, iron silicide, nickel oxide, andtungsten carbide. In another embodiment of the invention, the iMeHcomponent functions as the primary absorber of RF or microwave energy.When used with microwave enhancement, the iMeH component is sufficientlydispersed within the catalyst and feedstock combination to solve theproblem of hot spots and arcing generally associated with theintroduction of metals into a microwave or RF field.

The selective use of RF or microwave energy to drive the catalyticcomponent of the catalyst results in the direct reaction of the iMeHmonatomic hydrogen into the feedstock. It is cost effective to maximizethe use of fossil fuels to pre-heat the feedstocks to near reactiontemperatures, and use minimum RF or microwave energy to drive andcontrol the hydroprocessing reactions. Ideally there will be a minimizedor zero net temperature increase from the RF or microwave energy intothe catalyst support or into the feedstock because this energy isprimarily targeted into the iMeH to enhance the reaction exchange ofmonatomic hydrogen. Selective coupling of the RF or microwave energy isaccomplished through selection and control of the relative dielectricparameters of the catalyst's components and the feedstock. This resultsin efficient, economically viable catalytic processes, which areenhanced using microwaves.

The catalyst of the present invention may be used in all types ofhydroprocesses or as a more specific example to hydrocrack organiccompounds. In these processes, the feedstock, e.g. organic compounds,are contacted with an iMeH catalyst comprising a metal hydride capableof releasing monatomic hydrogen at its surface. The combination of theiMeH and feedstocks may be exposed to any number of process conditions,(such as temperature, pressure, and space velocity) suitable for adesired hydroprocessing reaction.

The catalyst enables hydroprocessing at milder conditions andsignificantly lower pressures. High reactivity, lower process pressures,and new degrees of selectivity and control using RF or microwavesprovide for improved products and lower capital equipment and operatingcosts.

In the present invention, iMeH catalyst compositions having thefollowing characteristics have been specifically identified:

-   -   High hydrogen storage capacity (Range from 0.01 wt %-7.5 wt %        hydrogen in catalyst)    -   High molecular hydrogen absorption and monatomic hydrogen        reaction rates (greater than 0.01 cc/min/gm), for given        temperature or pressure changes. Typical operating pressures and        temperatures can range from ambient to 1000 psig and ambient to        600° C. A typical value for hydrogen reaction rates is 1        cc/min/gm, and materials have been measured with values greater        than 50 cc/min/gm.    -   Temperature-dependent desorption pressure    -   Ability to undergo repeated hydrogenation cycling    -   Tolerance for impurities    -   Using the invention disclosed herein, iMeH catalysts with high        reaction rates can be designed for operation up to 3000 psi and        600° C.

The monatomic hydrogen provided in the presence of an iMeH catalystpermits higher reaction rates and milder reaction conditions to be usedfor a given process.

It is known that Pt and Pd dissociate molecular hydrogen into monatomichydrogen when it is adsorbed onto the surface of these metals. The iMeHmaterials of the present invention have this property as well. The iMeHmaterials also store or absorb the dissociated molecular hydrogen intothe bulk of the iMeH matrix as monatomic hydrogen whereas metals such asplatinum do not.

Interstitial metal hydrides are produced by preparing samples of theconstituent metals in the desired proportions, and combining them andheating them so that they melt together homogeneously to produce a metalalloy. The resulting metal alloy is then exposed to hydrogen at atemperature and pressure characteristic of the alloy so that the metalalloy takes up the hydrogen in monatomic form.

The iMeH materials of the present invention are typically prepared by avolumetric (gas to solid alloy) method at a known temperature andpressure using a stainless steel reactor. The metallic hydride willabsorb hydrogen with an exothermic reaction. This hydrogenation processis reversible according to the following chemical reaction schematic:Metal Alloy+H₂⇄iMeH+EnergyDuring this process, hydrogen atoms will occupy interstitial sites inthe alloy lattice.

The metal alloy from which an iMeH is produced can be prepared bymechanical or induction heated alloying processes. The metal alloy canbe stoichiometric or hyper-stoichiometric. Hyper-stoichiometriccompounds are compounds that exhibit wide compositional variations fromideal stoichiometry. Hyper-stoichiometric systems contain excesselements, which can significantly influence the phase stability of themetallic hydrides. The iMeH is produced from a metal alloy by subjectingthe alloy to hydrogen at a pressure and temperature that is acharacteristic of the particular alloy.

The iMeH catalysts of the present invention can be selected to have adesired lattice structure and thermodynamic properties, such as theapplied pressure and temperature at which they can be charged and theoperating pressure and temperature at which they can be discharged.These working thermodynamic parameters can be modified and fine tuned byan appropriate alloying method and therefore, the composition of thecatalysts can be designed for use in a particular catalytic process.

The present invention is directed to catalysts containing interstitialmetal hydrides. These hydrides are composed of alloyed metals combinedwith monatomic hydrogen that is stored interstitially within their metalalloy matrix. Multi-component metal alloys from which the iMeH catalystsof the present invention are produced include combinations of Group 4elements with Group 5, 6, 7, 8, 9, 10 and 11 elements (based on the 1990IUPAC system in which the columns are assigned the numbers 1 to 18).Also iMeH catalysts of this invention may be produced from alloysincluding all combinations of lanthanides (atomic numbers 58 to 71) withGroup 7, 8, 9, 10 and-11 elements. For example; the alloy may beA_(x)T_(y) in which A is one or more Group 4 elements and T is one ormore Group 5, 6, 7, 8, 9 10 and 11 elements. In another example, A isone or more lanthanides and T is one or more Group 7, 8, 9, 10 and 11elements. X and y are the composition values for the different elementsin each series. These alloys may take the form of crystalline oramorphous fine powders, and the resulting interstitial metal hydrideshave properties making them useful for hydroprocessing reactions inwhich the operating temperature ranges from ambient (20° C.) to 1000° C.and operating hydrogen pressures in the range from ambient (15 psi) to2000 psi.

The iMeH serves as a high density source of interstitial monatomicreactive hydrogen and can be combined with known hydroprocessingcatalysts such as noble metals, metal oxides, metal sulfides, zeoliticacid or base sites to further promote hydroprocessing of feedstocks suchas organic compounds. The iMeH materials can be combined with otherhydroprocessing materials in a variety of ways to build an optimizedcatalyst for a particular reaction or function. In general, the finerthe powders being mixed (e.g. support, iMeH), the higher the surfacearea and the more intimate the mixing. Key to the processing steps is tominimize the exposure of iMeH to oxygen and/or water vapor at elevatedtemperatures (above 25° C.) for extended periods of time. Exposure canbe minimized by use of desiccants and by blanketing atmospheres of inertgases such as nitrogen and argon. The iMeH is not calcined or subjectedto an oxidizing environment at elevated temperatures.

Hydroprocessing catalysts and their respective components can take manyforms and structures. Much is known about optimizing catalystperformance based upon process requirements (e.g., hydrogenation,hydrocracking, hydrodesulfurization (HDS), hydrodemetallization (HDM),and hydrodenitrogenation (HDN). For example, the catalyst can be used asa powder, extrudate, or preformed matrix based upon the type of reactordesign selected (e.g., fluidized bed, fixed bed, catalytic converter,etc.)

The simplest iMeH catalyst is the iMeH powder itself. In this case theiMeH provides monatomic hydrogen and is the catalyst forhydroprocessing. The process and reactor hardware are more complex thanin a fixed catalyst bed process.

The iMeH catalysts of the present invention, when used in powder form,may be mixed and dispersed within the feedstock and transported througha reactor (e.g. slurry reactor). After the desired reaction has beencatalyzed in the reactor, the iMeH powder is then separated from thereaction products for reuse.

An iMeH can be combined with a support and optionally other catalyticelements to produce a composite catalyst. The support provides for thephysical dispersion of iMeH, providing greater surface area and ease ofhandling. The support also serves to increase the surface area of theactive catalytic elements and thereby increase the process reactionrates. The support also serves to disperse the metallic or metal oxidecatalytic sites so as to prevent arcing in the presence of a strongelectric or magnetic fields that may be used to expedite catalyticaction.

The iMeH compounds of the present invention can be utilized in acrystalline or amorphous form. The support may be composed of aninorganic oxide, a metal, a carbon, or combinations of these materials.The iMeH phases and catalytic elements can be dispersed as mechanicallymixed powders, or can be chemically dispersed, impregnated or deposited.When mixed powders are used in the present invention, the powderparticle size is controlled to provide a powder that has particles thatare small enough to provide suitable surface area and reactivity, butnot so fine as to produce significant surface oxidation. In oneembodiment, particles used in the catalyst of the present invention havediameters ranging from about 0.01 micrometers to about 1000 micrometers,from about 0.1 micrometers to about 100 micrometers, or from about 1micrometer to about 10 micrometers. Nanosize powders and nanostructuralelements containing an iMeH have also been found to be useful. The othercatalytic elements may be known catalysts such as noble metals such asplatinum or palladium, metal oxides, metal sulfides, and zeolite acid orbase sites; these additional catalytic elements can further promotehydroprocessing. A hydroprocessing component and a hydrocrackingcomponent used in combination with the iMeH may be one or more of thesecatalytic elements. Both the combination of an iMeH powder with asupport, which can provide an additional catalyst function (i.e. atcatalytically active or inert support), or an iMeH dispersed onto ahydroprocessing catalytic powder, can be especially effective forhydrocracking in an FCC type of fluidized bed reactor.

The iMeH catalysts of the present invention can also be coated onto anextrudate, typically formed from a mixed metal oxide such as alumina orsilica. This method has practical manufacturing advantages, provides auniform coating, and yields a high iMeH surface area. The iMeH can becoated onto the spheres, pellets, rings, cylinders, and extrudates ofother shapes, including 3-lobed and 4-lobed extrudates, of whichcommercial catalysts are typically formed. The iMeH catalysts can alsobe incorporated into the body of the extrudate. A powder of iMeH may bemixed with inert support powder, such as silica or alumina, or acommercial hydroprocessing catalyst, commercial hydrotreating catalystor commercial hydrocracking catalyst ground to a fine powder. The mixedpowder is combined with a binder and extruded. Fine powder large porealumina coated with metal sulfides such as CoMoS_(x), or zeolite powdercoated with a noble metal such as palladium or platinum may also becombined with iMeH in this fashion.

The order of catalyst fabrication is based on minimizing exposure of theiMeH to oxygen or water vapor. It has been found that chemically coatinga mixed metal oxide form, such as an extrudate, with iMeH has severalmanufacturing advantages, provides for a more uniform coating, andshould yield the highest practical iMeH surface area.

In a typical process for the production of a catalyst of the presentinvention incorporating an extrudate, the raw inorganic oxides materialsare extruded and calcined, the extrudate is chemically coated withhydroprocessing metals such as Ni/Mo or Pd and the resulting combinationis calcined. Finally, the extrudate is chemically coated with an iMeHand treated with hydrogen.

The iMeH of the present invention can be combined by many means withexisting hydroprocessing catalysts or components.

FIG. 1 depicts the process steps for the production of a catalyst of thepresent invention detailing the iMeH powder processing steps prior tomixing with the hydroprocessing catalyst powder. A metal alloy, ofselected composition, is first exposed to hydrogen to produce aninterstitial metal hydride structure. Based on available equipment, theiMeH is then reduced to powder form, under an inert or hydrogenatmosphere using any one of several conventional powder processingtechniques known to those skilled in the arts. Alternatively, the metalalloy can first be made into a powder and then exposed to hydrogen toproduce iMeH powder. The iMeH powder is then intimately mixed with ahydroprocessing catalyst powder and formed into a catalyst structure.The catalyst may take the form of an extrudate (including three-lobedand four-lobed forms), sphere, pellet, ring, cylinder, or other shapes,including a powder of particle size differing from, the powder sizes ofthe starting powders. After forming, the iMeH is activated by exposureto hydrogen at temperature and pressure appropriate to the iMeHcomposition.

FIG. 2 depicts the process steps, as an example, in the production of acatalyst of the present invention in which an iMeH powder is mixed witha hydroprocessing catalyst powder. The hydroprocessing catalyst powdercan be manufactured, by those skilled in the art, based upon processrequirements. FIG. 2 shows several possibilities consisting of a supportpowder (such as a zeolite) coated with a noble metal catalyst and/or ametal sulfide such as NiMoS_(x).

FIG. 3 depicts the process steps in the production of a catalyst of thepresent invention in which an iMeH is coated on a hydroprocessingcatalyst form. The hydroprocessing catalyst form can be manufactured, bythose skilled in the art, based upon process requirements. The iMeHcoating can be produced by methods including, but not limited to,chemical vapor deposition (CVD), chemical coating, ion implanting, andsputtering. Hydrotreating catalyst or hydrocracking catalyst may besubstituted for the hydroprocessing catalyst.

FIG. 4 depicts the process steps in the production of a catalystdetailing but not limiting the present invention in which an iMeH iscoated on a hydroprocessing catalyst form. The hydroprocessing catalystform can be manufactured, by those skilled in the art, based uponprocess requirements. FIG. 4 elaborates several possibilities consistingof a support form coated with a noble metal catalyst and/or a metalsulfide such as NiMoS_(x).

Properties of the support such as porosity, pore size distribution,surface area and acidity are selected on the basis of the feedstock andthe selected hydroprocess. For low molecular weight organic compounds,microporous supports are appropriate because they offer fine pore sizeand high surface area. For heavier organic compounds a larger pore mesoand/or macroporous catalyst structure are required to allow the largermolecular size organic compounds to enter. The acidity can be adjustedto a level suitable for the particular process being catalyzed.

The iMeH can be combined with or placed in proximity to one or moreadditional catalytic elements or components, such as a cracking catalystor a hydroprocessing catalyst. This combination reduces the severity ofthe conditions required for hydroprocessing. Pd, Ni/Mo, W, and Co/Mocatalysts are examples of materials that can function as theseadditional catalytic elements or components. The support function andadditional catalytic properties can be combined in a single substance.The iMeH may, if it is placed in close enough contact with theadditional catalytic elements, supply them with monatomic hydrogen,thereby increasing their catalytic activity. The additional catalyticelements need not be capable of storing monatomic hydrogen in theirmatrix to exhibit increased catalytic activity through the donation ofmonatomic hydrogen from the iMeH.

Another means of increasing catalytic activity is by enhancement throughthe hydrogen spillover effect. Without intending to be limited by thisdescription, the hydrogen spillover effect generally refers to thephenomenon when adsorbed hydrogen on the catalyst (metal) surfacemigrates to a nearby catalytic site, or into the interstitial volume ofthe support. The iMeH produces monatomic hydrogen, which may not beimmediately reacted with, but not limited to, the organic compound feed.Noble metal catalysts such as palladium and platinum can assist themigration of the reactive monatomic hydrogen. These noble metals havebeen shown to be novel promoters in combination with iMeH therebyincreasing the catalytic effect. This is thought to be due to thehydrogen spillover effect, which increases the effective catalystsurface area.

A specific example of such a combined catalyst contains zeolite,palladium and iMeH which can enhance hydrogenation reactions. iMeH inpowder form has a lower surface area compared to chemically coatedpalladium on the zeolite support. The iMeH in powder form can be anorder of magnitude larger in size than the palladium particles dispersedon the support. The catalytic reaction site is thought to be extendedbeyond the surface of the iMeH through the transport of the monatomichydrogen by means of the palladium enhanced hydrogen spillover effect.

Monatomic hydrogen is a highly reactive species and will react with manyspecies as well as with another hydrogen atom to form molecularhydrogen. Therefore, intimate contact between the iMeH and the feedstockbeing hydroprocessed has been found to be significant. For example, ifan oxide layer exists on the iMeH surface, the monatomic hydrogen islikely to react within the oxide layer before it encounters and reactswith a feedstock molecule. The iMeH used in the present invention isessentially free from surface oxides; an iMeH having a significant oxidecoating cannot supply any significant amounts of monatomic hydrogen to achemical process occurring on the oxide coating. The extent of the zonein which monatomic hydrogen can be found near the iMeH surface changeswith process conditions that affect the mobility and reactivity of themonatomic hydrogen. The surface of the catalyst of the present inventionis kept essentially free of oxides by avoiding exposure of the catalyticsurface to air, any other oxidizing agent or water vapor at elevatedtemperatures. For certain highly reactive catalysts of the presentinvention, contact with air, any other oxidizing agent or water vapor isavoided at ambient temperatures as well as elevated temperatures.Experimental results have confirmed that minimizing the amount ofsurface oxides present increases the activity of the catalyst of thepresent invention. For iMeH powders or dispersions, the finer theparticle size, the thinner the surface oxide layer requirements. Thesurface oxide thickness should not exceed half the diameter of the iMeHparticle, preferably being one quarter the diameter or less, optimallybeing one-tenth the diameter or less. As an example, with an iMeHparticle, with a diameter of one micrometer, the oxide layer wouldoptimally be 100 nm or less.

It has also been found that surface condition of the iMeH is related tothe state of matter of feedstocks that can be catalyzed. It has beenfound that the catalysts of the present invention are able to processliquid feedstocks as well as gaseous feedstocks.

The present invention has been found to be particularly useful in thehydroprocessing of organic compounds at lower pressures thanconventional catalysts for a particular process.

According to the present invention, iMeH catalysts have been found to beof particular utility in catalyzing reactions involving the addition orrearrangement of hydrogen atoms in chemical species. It is expected thatthe catalyst of the present invention will catalyze reactions ofinorganic materials in which hydrogen is involved. In particular, thecracking and hydroprocessing of petrochemicals is expedited by iMeHcatalysts. Organic compounds are defined as compounds of carbon. Otherelements that may be included in organic compounds include hydrogen,oxygen, nitrogen, sulfur, phosphorus, halogens, and metals. Classes oforganic compounds include aliphatic compounds, including straight chainand cyclic alkanes, olefins, and acetylenes, aromatic compounds,including polycyclic structures, oxygen bearing compounds, includingalcohols, ethers, aldehydes, ketones, carboxylic acids, esters,glycerides, and carbohydrates, nitrogen bearing compounds, includingamines, amides, pyrroles, and porphyrins, sulfur bearing compounds,including thiols, sulfides, and thiophenes, phosphorus bearingcompounds, including phosphate esters, organo-metallic compounds, andcompounds with halogens, such as fluorine and chlorine. The followingterms are used in the description of processes in which the presentinvention can be practiced:

-   -   Hydroprocessing—General term used to describe all catalytic        processes involving hydrogen. Includes the reaction of any        petroleum fraction with hydrogen in the presence of a catalyst.        Examples include hydrocracking, hydrotreating and        hydrodesulfurization.    -   Hydrocracking—A process used to convert heavier feedstocks into        lower-boiling, higher-value products. The process employs high        pressure, high temperature, a catalyst, and hydrogen. Typically        50% or more of the feed is reduced in molecular size.    -   Dewaxing—The process of removing waxes from a processed oil        stream in order to improve low temperature properties. Waxes are        high molecular weight saturated hydrocarbons or paraffins,        typically those that are solids at room temperature. Dewaxing        can be accomplished by solvent separation, chilling and        filtering. The catalytic dewaxing process uses one or two        zeolite catalysts to selectively hydrocrack the waxes into lower        molecular weight materials.    -   Catalytic Dewaxing—A catalytic hydrocracking process which uses        molecular sieves to selectively hydrocrack the waxes present        into hydrocarbon fractions. This process is also referred to as        hydrodewaxing.    -   Hydrotreating—Processes which remove undesirable impurities such        as sulfur, nitrogen, metals, and unsaturated compounds in the        presence of hydrogen and a catalyst. In contrast with        hydrocracking, essentially none of the feed is reduced in        molecular size in hydrotreating.    -   Hydrodenitrogenation—A hydrotreating process in which the        nitrogen species which are present in heavier distillates are        removed.    -   Hydrodemetalization (HDM)—A hydrotreating process in which metal        species, typically nickel and vanadium, which are present in        heavier distillates are removed.    -   Hydrodesulfurization (HDS)—A catalytic process in which the        principal purpose is to remove sulfur from petroleum fractions        in the presence of hydrogen.    -   Feedstock—Petroleum fraction subjected to a treatment process,        including hydroprocessing and cracking.    -   Cracking—The conversion of feedstocks into lighter products.

Conventional catalysts show increased activity with increasedtemperature, and are generally subjected to thermally-conductedconventional heating to increase temperatures. Selected catalysts canalso be heated dielectrically. Dielectric heating refers to a broadrange of electromagnetic heating, either magnetically or electric fieldcoupled, and includes radio frequency (RF) heating and microwaveheating. It has been found that the value added for the process ismaximized by using a minimum of dielectrically coupled energy, and byusing conventional heat to supplement the total process energy. In apreferred embodiment of the present invention, microwave or RF energy isused in conjunction with fuel-fired heating or resistive heating. Theexclusive use of microwave heating or RF heating, in the absence offuel-fired heating or resistive heating, is not an economically viableprocess. In the present process, the primary effect provided bymicrowave and RF energy is the enhancement of the catalyzed chemicalreaction, rather than the indirect effect of heating.

In a preferred embodiment of the present invention when used withmicrowave enhancement, the iMeH is in direct contact with a support; theiMeH functions as the primary microwave absorption material and no othermicrowave absorbing component is needed in the catalyst. If the iMeH issuitably dispersed, for example in a slurry comprising a feedstock andiMeH, it may be used in the absence of a separate support material.

The dielectric parameter called the loss tangent is known by thoseskilled in the art to measure the relative RF or microwave energy that aparticular material absorbs at a given frequency. The loss tangent, alsocalled the loss factor, is the ratio of the energy lost to the energystored. A larger loss tangent for a material means that more energy isabsorbed relative to a material with a lower loss tangent. Thedielectric absorption of energy can cause different materials to heat atsubstantially different rates and to achieve considerably differenttemperatures within the same RF or microwave field.

The dielectrically absorbed energy can also directly contribute to theprocess energy balance. When used to drive an endothermic reaction, suchas a cracking reaction, this means that if the absorbed RF or microwaveenergy equals the heat-of-reaction cracking energy, then there will notbe a net increase in the bulk temperature for the process. However ifmore RF or microwave energy is absorbed than is necessary for thecracking reaction, or if there is a resulting exothermic reaction, e.g.hydrogenation from the release of monatomic hydrogen, then there will bea net increase in the bulk temperature.

In the preferred embodiment, for use with microwave and RF enhancement,the iMeH catalytic material is selected to have a higher loss factorthan the catalyst support or other materials comprising the catalyst. Inthis preferred embodiment, the iMeH catalyst combines the two attributesof: 1) iMeH catalytically active sites and 2) iMeH material being theprimary microwave and RF energy absorber due to its higher loss factorthan other materials comprising the catalyst. This embodiment of thepresent invention has been found to produce higher reaction efficienciesthan previously obtained.

In another embodiment of the invention, the iMeH is the primary absorberof microwave or RF energy, but one or more other secondary microwaveabsorbing components are present. In yet another embodiment of theinvention, the iMeH is not the primary absorber of microwave or RFenergy and does not have the highest loss factor, but the iMeH materialis in direct thermal contact with materials that are the primaryabsorbers of microwave or RF energy and have higher loss factors.

Loss factors for the bulk iMeH catalyst of 0.30 or less, particularly0.20 or less, such as 0.01 to 0.20, have been found to enhancereactions, while minimizing nonselective heating of the feedstock. Thisconsideration for loss factor values maximizes the penetration depth ofRF or microwaves, enabling the process of the present invention to becarried out on a large scale. In the preferred embodiment the lossfactor for the iMeH, in combination with the support or bulk of thecatalyst, is greater than that of the feedstock. Therefore the energygoes into catalyzing the reaction rather than the nonselective heatingof the feedstock. The penetration depth is also a function of frequency.

The combined use of iMeH catalyst along with microwave or RF energycomprises two new process variables with which to optimize catalytichydroprocessing. The iMeH serves as a high density source ofinterstitial monatomic reactive hydrogen. The application of microwaveor RF energy provides a means of controlling the reaction of iMeHmonatomic hydrogen with the feedstock. Also, proper application ofmicrowave or RF energy promotes higher flux exchange of monatomichydrogen from the matrix and further enhances the hydroprocessingreactions. This also controls and promotes the adsorption of molecularhydrogen to be dissociated into monatomic hydrogen. More specifically,the proper application includes control of the microwave or RF intensityor field strength, frequency, and making use of modulation techniques.Control of these parameters, in particular, using any number ofmodulation techniques known to those skilled in the art, for exampleamplitude modulation, frequency modulation and pulse width modulation,is of great utility to precisely control or to maximize the fluxexchange of monatomic hydrogen from the iMeH to react with organiccompounds.

Alternatively, the catalyst of the present invention may contain aseparate microwave absorption material in combination with the iMeH. Thesupport may be catalytically inactive or active. If the support iscatalytically active, its activity may be enhanced by the production ofmonatomic hydrogen by the iMeH, with which the support is in closecontact.

An iMeH catalyst used in combination with microwave energy can beconfigured in a variety of ways to produce a catalyst optimized for aparticular reaction or function. If a more intimate mixture is desired,so that the iMeH and the support are in closer contact, finer powders,sub-micron or nano-particles, can be used; and would also increasecatalytic surface area.

In the present invention, monatomic hydrogen, which can also bedescribed as interstitial (dissociated) atomic-hydrogen radicals, fromwithin the matrix of the iMeH is used for the hydrogenation of organiccompounds and their derivatives. These dissociated monatomic hydrogenradicals are not covalently or ionically bound to metal atoms within theiMeH. The population of these free monatomic hydrogen radicals isgenerally in equilibrium between the interstitial hydrogen of theselected iMeH and its surface. This equilibrium is governed by factorsof iMeH structure, temperature, pressure, and field strength of theradio frequency or microwave energy. The absorption of monatomichydrogen by the crystal lattice of the iMeH is an exothermic reaction.The surface monatomic hydrogen radicals, in equilibrium with theinterstitial matrix of the iMeH, may be directly reacted with organiccompounds and their derivatives contacted at or near the surface of theiMeH. It is believed, without wishing to be bound by thischaracterization of the invention, that this hydrogenation happensbecause a localized high density of monatomic hydrogen radicals resultsin reactivity equivalent to or higher than that produced bynon-localized high density of molecular hydrogen exerted by highhydrogen pressure. Hydrogen is more reactive with the C—C bond when itis in a radical monatomic form than when it is in the form of a diatomicmolecule. Catalytic reactions involving an iMeH can provide aperformance equivalent or better to that of a high-pressure zone ofmolecular hydrogen.

The processes of the present application, even though they may notresult in an increase in the hydrogen content of the product, depend onhydrogen availability for two reasons: 1) hydrogen availability preventspoisoning of catalyst, and 2) hydrogen availability is a key factorpermitting molecules to undergo rearrangement. Ideally, a moleculebinding to an active catalytic site undergoes the desired reaction orrearrangement and leaves the catalytic surface. However, if there is alocal deficiency of hydrogen, the molecule may polymerize, react withanother active molecule, or deposit on the catalytic surface as coke;all three of these outcomes can reduce the number of available catalyticsites. In the absence of hydrogen, the catalyst becomes deactivated morerapidly and requires more frequent cycling. Because the catalyst of thepresent invention can provide hydrogen from its own structure as well asaccommodate hydrogen from the reaction medium, problems of localizedhydrogen deficiency are minimized. In addition, because of its abilityto stabilize monatomic hydrogen, the catalyst of the present inventionis able to promote reactions in which hydrogen atoms are added to thefeedstock molecules.

Test results indicate that it is important to balance the hydrogenationwith other catalytic functions such as cracking or desulfurization so asto minimize undesired reactions like coking. This balance is achieved bycontrolling the ratio of iMeH content and its respective surface area tothe content and surface area of the support and other catalyticcomponents.

The present invention has been also found to be particularly useful inthe cracking or hydrocracking of heavy organic compounds. The dielectricproperties of heavy organic compounds allow them to be selectivelyheated by RF and microwave heating. If they crack near the surface ofthe iMeH, then they will react with monatomic hydrogen and undergohydrogenation, desulfurization, and other desired processes. Theproducts of the cracking reaction have lower microwave loss factors thando the reactants, and are thus less subject to undergo RF and microwaveheating than the reactants. The reactants are therefore selectivelyheated and selectively reacted, resulting in enhanced processefficiency.

Compositions of iMeH

The following are examples of catalyst compositions according to thepresent invention:

Cat 100

-   AT₅-Type-   Crystal structure: Hexagonal-   General formula: A_(1-x)M_(x)T_(5-y-z)B_(y)C_(z)

x=0.0-1.0, y=0.0-2.5, z=0.0-0.5

A=Mm (mischmetal); T=Ni; M=La, Pr, Nd or Ce; B═Co; C═Mn, Al or Cr

Cat 200

-   A₂T₁₄B-Type-   Crystal structure: Tetragonal-   General formula: A_(2-x)M_(x)T_(14-y)C_(y)D_(z)B

x=0.0-2.0, y=0.0-14, z=0.0-3.0

A=Nd or Pr; T=Fe; M=La, Pr, Nd or Ce; B=Boron; C═Co; D=Cr, Ni or Mn

Cat 300

-   A₂T-Type-   Crystal structure: Monoclinic-   General formula: A_(2-x)M_(x)T_(1-y)B_(y)

x=0.0-0.5, y=0.0-0.5

A=Mg; T=Ni or Cu; M=La; B═Fe or Co

Catalysts of the present invention may also contain combinations ofthese compositions.

The catalyst of the present invention may be used with all varieties ofprocess reactor configurations, which are known to those skilled in theart. Generally common to these configurations are a reaction vesseldesigned to permit the introduction of gas and liquid, to contain thefeedstock and the catalyst at a suitable pressure and temperature, andthat accommodates the removal of product, as shown in FIG. 5.Alternatively either gas and/or liquid may be pre-heated, depending uponprocess conditions, as is common practice to those skilled in the art.The catalyst is introduced into the reaction vessel under conditionspreventing the formation of surface oxides. Depending on the reactivityof the catalyst, exposure of the catalyst to oxygen or water vapor athigh temperature may be avoided, or an inert atmosphere may be used toblanket the catalyst. The catalyst may take the form of a bed in thereaction vessel, or the catalyst and feedstock may be circulated so thatthey are in close contact with each other during processing, resultingin a catalyst-feedstock (catalyst-organic compound) mixture. It is knownto those skilled in the art that other types of reactor catalyst bedsare possible, e.g. fixed beds, moving beds, slurry reactors, fluidizedbeds. Preferably, provision is made for recirculating hydrogen duringthe catalytic process. Reaction occurs on introduction of feedstock andhydrogen gas on to catalyst within the reaction vessel. The feedstock(organic compounds) reacts with the monatomic hydrogen at the surface ofthe catalyst. Energy is applied to the catalyst, feedstock (organiccompound), reaction mixture or the catalyst-feedstock (catalyst-organiccompound) mixture; these may be heated by heat resulting from a chemicalreaction such as combustion, by resistive heating or by acousticheating, may be heated dielectrically by radio frequency or microwaveenergy, or they may be heated by a combination of these methods.Combustion is the chemical combination of a substance with oxygen.Resistive heating is heating resulting from the flow of a currentthrough an electrical conductor. Acoustic heating is heating resultingfrom physical motion or vibration induced in a sample, with a sonicfrequency of less than about 25 KHz, or an ultrasonic frequency greaterthan about 25 KHz, typically 40 KHz. Radio frequencies range from about3×10⁵ Hz to about 3×10⁸ Hz; microwave frequencies range from about 3×10⁸Hz to about 3×10¹² Hz. Cooling mechanisms known to those skilled in theart may be combined with the reaction vessel to accommodate exothermicreactions (e.g. the introduction of quenching gases or liquids). Thereaction products may be recovered upon their removal from the vessel.The feedstock (organic compounds) may be preheated before contact or incombination with the catalyst by heat resulting from a chemical reactionsuch as combustion, by resistive heating or by acoustic heating, or maybe heated dielectrically by radio frequency or microwave energy.

The catalyst of the present invention may be used with all varieties ofprocesses that are known to those skilled in the art. Typical processconditions include temperatures of at least about 150° C., moreparticularly, at least about 225° C., and even more particularly, atleast about 300° C. Generally, the methods are carried out attemperatures less than about 600° C., more particularly, less than about550° C., and even more particularly, less than about 450° C. Thepressure at which the methods may be practiced are generally at leastambient pressure (14.7 psia), more particularly, at least about positive25 psig, and even more particularly, at least about positive 50 psig.Typically, the pressure is less than about positive 600 psig, moreparticularly, less than a positive pressure of about 450 psig, and evenmore particularly, less than a positive pressure of about 300 psig. RFor microwave energy at a frequency greater than or equal to about 1 MHz,and more particularly, at least about 500 MHz may generally be applied.RF or microwave energy at a frequency less than about 10,000 MHz, andmore particularly less than about 3,000 MHz, of RF or microwave energymay be generally applied. The liquid hourly space velocity (LHSV)defines the feedstock to catalyst ratio. LHSV is the liquid hourly spacevelocity defined as the ratio of the volume of feedstock to the volumeof catalyst that passes through the catalyst on an hourly basis. TheLHSV range is generally at least about 0.10 per hour, and moreparticularly at least about 0.20 per hour, and even more particularlyabout 0.30 per hour. The LHSV tends to be less than about 10 per hour,and more specifically, less than about 5 per hour, and even morespecifically, less than about 3 per hour.

Batch process reactors accommodating the catalyst and process of thepresent invention operate at elevated temperature and pressure. Thebatch process may have means to heat and/or cool the reactor, add andremove catalyst, receive feedstock and gas, and remove product and gas.Preferred configurations include a means to stir or recirculate the gas,catalyst and feedstock, a means to recharge the catalyst, and a means toprovide RF or microwaves to the reaction site.

The preferred embodiment is a continuous flow process. Continuous flowreactors accommodating the catalyst and process of the present inventionoperate at elevated temperature and pressure. They may contain means toheat and/or cool the reactor, add and remove catalyst, receive feedstockand gas, preheat feedstock and gas, and remove product and gas.Preferred configurations include a means to stir or recirculate the gas,catalyst and feedstock, a means to recharge the catalyst, and a means toprovide RF or microwaves to the reaction site.

Recirculation capabilities add to the utility of reactors used in thepresent invention. FIG. 6 depicts the use of a reactor with thecapability of preheating the gas and liquid and recirculating thereaction mixture or components of the reaction mixture internally andexternally. FIG. 7 depicts the use of a reactor with the capability ofrecirculating the reaction mixture or components of the reaction mixtureinternally and externally, as well as the capability of recirculatingthe catalyst for regeneration or recharging. The catalyst recirculationloop for regeneration or recharge can stand alone as seen in option 1 orbe combined with existing loops as seen in options 2 or 3. FIG. 8depicts improved handling of the output for any reactor design of theprocess for the present invention having the capability of separatingproduct into gas and liquid. The option shown in FIG. 8 can be used withany of the reactors shown in FIGS. 5, 6, and 7. FIG. 9 depicts improvedhandling of the output for any reactor design of the process for thepresent invention having the capability of gas product collection, gasproduct recycling, liquid product collection and liquid productrecycling and a means for injecting the gas and liquid to be recycledand injected back into the feed or input stream. The option shown inFIG. 9 can be used with any of the reactors shown in FIGS. 5, 6, and 7.

EXAMPLE 1

Logarithmic Pressure Composition Isotherms of an iMeH Catalyst

FIG. 10 shows the logarithmic pressure composition isotherms for themonatomic hydrogen desorption curve of iMeH Cat 100,Mm_((1.1))Ni_((4.22))Co_((0.42))Al_((0.15))Mn_((0.15)). The plotdisplays the results at constant temperatures and equilibrium conditionsfor Cat 100 powder, relating pressure and stored iMeH hydrogen density.The plot shows that at a constant temperature, the iMeH hydrogen densityincreases as a non-linear function of pressure. The plot also shows thatdecreasing the temperature of the isotherms results in an increase ofthe iMeH hydrogen density. This data characterizes the iMeH catalyst'shydrogen capacity to provide monatomic hydrogen for hydrogenation orhydroprocessing reactions.

EXAMPLE 2

Selection of an iMeH Catalyst

To select an iMeH for a catalytic process, and to determine theoperating parameters, it is useful to know how much hydrogen an iMeHmaterial stores, the temperature at which the monatomic hydrogendesorbs, and the effect of pressure on monatomic hydrogen desorption.

In FIG. 11, plots of total hydrogen capacity versus temperature atambient pressure are shown for Cat 100, Cat 200 and Cat 300, threeexample catalysts of the present invention. The compositions of theseexamples of iMeH catalysts according to the present invention are asfollows:

Cat 100Mm_((1.1))Ni_((4.22))Co_((0.42))Al_((0.5))Mn_((0.5))Cat 200Nd_((2.05))Dy_((0.25))Fe_((1.3))B_((1.05))Cat 300Mg_((0.05))Ni_((0.95))Cu_((0.07))

Given the standard industrial tolerances in the production of metals itis expected that very similar properties will be exhibited by acomposition with the following general formulas:

Cat 100Mm_((30-34.5))(Ni, Co, Al, Mn)_((69.9-66.4))Cat 200(Nd, Dy)_((15.5-6.5))(Fe, B)_((83.5-84.5))Cat 300Mg₍₄₄₋₄₆₎(Ni, Cu)₍₅₄₋₅₆₎

Monatomic hydrogen desorbs from Cat 100 at lower temperatures, below200° C. while monatomic hydrogen desorbs from Cat 300 at temperaturesabove 250° C. Also, the transition for desorption for Cat 300 issharper. Thus, for a reaction at ambient pressure, one would select Cat100 for a low temperature reaction below 200° C. and Cat 300 for ahigher temperature reaction above 300° C. Cat 200, while it has a lowertotal hydrogen capacity, has the property of desorbing monatomichydrogen over an extended temperature range.

When the pressure is adjusted, the operating temperature that optimizesthe release of monatomic hydrogen is changed. Table 1 shows that at agiven temperature, less monatomic hydrogen is released as the operatingpressure increases. Therefore, selection of iMeH depends upon bothprocess temperature and pressure. The hydrogenation performance of theiMeH can be controlled by the operating parameters so that, in thisexample, the low temperature iMeH can be used at higher temperatures byincreasing the process pressure, within its thermodynamic limit.

EXAMPLE 3

Microwave Enhanced Hydroprocessing with Respect to Feedstock

For heavy oils, such as pitch residuum, microwave energy ispreferentially absorbed by the aromatic and polar compounds in the oilthereby promoting their reaction. This is shown in FIG. 12 where theloss tangent (y-axis) for pitch residuum is approximately an order ofmagnitude greater than for microwave processed pitch (reduced molecularweight and lower boiling point) across a wide range of microwavefrequencies (0.5-2.8 GHz). The loss tangent, also called loss factor orthe dissipation factor, is a measure of the material's microwaveadsorption. The loss tangent is also the ratio of the energy lost to theenergy stored.

In hydroprocessing according to the present invention, the propercontrol and use of the dielectric loss tangent leads to the efficientuse of microwave energy. The fraction of microwave energy, which isabsorbed by any component of the oil and catalyst mixture, can beefficiently controlled. For example, when the dielectric loss tangent ofthe catalyst is equal to the oil, then approximately half the microwaveenergy initially goes into heating the oil and half into the catalyst.The primary method of loss tangent control is by adjusting the materialcompositions of the individual components. This includes theoptimization of catalyst composition or the blending of feedstocks.

In the case where increased hydrogenation is desirable, hydrogenationcan be enhanced by increasing the loss tangent of the iMeH catalystcomponent relative to that of the oil. For heavy oils, as the oil isreacted from residuum to cracked oil, on a local scale, more of themicrowave energy, as further explained in example 5 and shown in FIG.13, is available to go into the catalyst, further promotinghydrogenation enhancement, in comparison to thermal heating of the oil.

When lighter oil is being hydrogenated, the oil itself would alreadyhave a lower loss tangent. In this case the catalyst can be adjusted tomaintain a high fixed loss tangent ratio of the catalyst to the oil.Microwave energy can thereby be efficiently directed to promotehydrogenation by the coupling into the hydrogenation components of thecatalyst.

Methods for adjusting the catalyst loss tangent include, but are notlimited to, controlling iMeH dispersion, iMeH concentration, andselection of iMeH alloy type or composition and/or type. Similarmodification to the support structure can be made as well as doping andcoating with selected materials.

Similarly hydrocracking can be controlled through the adjustment of thedielectric properties of the catalyst. Microwave energy can beefficiently directed to promote cracking by the coupling into thehydrocracking components of the catalyst.

EXAMPLE 4

Evaluation of Microwave Assisted Processing of Heavy Petroleum Fractions

The feed samples used for this example were pitch residuum, heavyresidue left after straight run atmospheric distillation in theproduction of gasoline and diesel fuels. The samples were processed,using microwave energy at 2.45 GHz, slightly below ambient pressuresunder a blanket of nitrogen. Several types of commercially availablezeolites were used as catalysts: 5A, 13X, and ammonium Y. Spot checks ofthe bulk temperature of the catalyst/pitch mixture were conducted usinga type K thermocouple. Temperatures ranged from about 200° C. to 475° C.Temperature checks were conducted as rapidly as possible after themicrowave power was turned off, typically within five to ten seconds, tominimize cooling of the sample.

These tests show the effect of using only a simple catalyst without theaddition of iMeH catalyst. The properties of the feed (pitch residuum)and the product (microwave processed pitch) are shown in Table 2.Microwave processing of the feed reduced the pour point reduced from 95to 30 and the viscosity was lowered from 413 cSt at 100° C. to 7 cSt at50° C. Additionally, the simulated distillation results show that theboiling point distribution has significantly shifted from mostly highboiling organic compounds, in the pitch feed, to lower boiling organiccompounds in the product. Little change was observed in either thespecific gravity or in the concentration of sulfur. This indicates thatwithout the use of an improved catalyst, the product was produced viacracking reactions. There was little desulfurization or addition ofhydrogen.

In another series of tests the pitch was microwave processed with andwithout iMeH catalyst in a microwave oven to evaluate the effect of theiMeH catalyst component while using the pitch feedstock. Tests wereperformed with the following catalyst mixtures; 1) commercial 13Xzeolite, 2) a mixture of commercially available 13X zeolite andammonia-Y catalyst, and 3) a mixture commercial sodium-Y catalyst withiMeH Cat 100. As before, the samples were processed slightly belowambient pressures under a blanket of nitrogen at an approximatetemperature of 250° C. Lead acetate paper was positioned near thereaction vessel outlet to determine the presence hydrogen sulfide (H₂S).

Only the tests using catalyst with the iMeH Cat 100 component rapidlyturned the lead acetate paper black, indicating that large quantities ofhydrogen sulfide were being produced and the product was beingdesulfurized. No H₂S was detected during tests conducted with catalystswithout the iMeH Cat 100 component.

The stored monatomic hydrogen within the iMeH catalyst was the onlysource of free hydrogen. These tests show that the iMeH catalystcomponent, with the enhancement of the microwave energy, assists thecatalytic hydrogenation and release of H₂S to promote desulfurization.These tests show that microwave energy and iMeH catalyst promotehydrogenation and hydroprocessing at low pressure.

EXAMPLE 5

Description of Microwave Enhanced Hydrogenation with Respect to iMeHCatalyst

FIG. 13 depicts measurements obtained in a batch reactor test. In thistest, 30 cc of iMeH catalyst (50% Cat 300/50% USY (1% Pd) was placed ina reactor with 30 cc of coker-kero feed. This feedstock has both sulfurand aromatic components. The reactor pressure, microwave power at 2.45GHz, and the iMeH catalyst bulk temperature were monitored along withthe H₂ flow rate into the reactor. The initial pressure was set at 50psig. Upon heating to 200° C. the pressure increased to 60 psig where itwas maintained throughout the test.

FIG. 13 shows that, when the microwaves are applied into the reactor,the flow of gaseous molecular hydrogen (H₂) into the reactor is zero.For this example of feedstock, catalyst, temperature, and low pressure,hydrogenation occurs only when monatomic hydrogen (H•) is reacted intothe coker-kero feedstock through the effects of both the iMeH catalystand the microwaves. The data shows that the pressure remains eitherconstant or is slightly reduced during the time when the microwaves areon. Hydrogenation occurs when the microwave field simultaneouslystimulates the iMeH and causes the direct reaction of the monatomichydrogen (H•), from within the interstitial lattice of the iMeH, tocatalyze and combine with the coker-kero hydrocarbons and sulfurcompounds comprising the feedstock. This direct catalytic reactionhowever temporarily depletes the monatomic hydrogen (H•) from within theinterstitial lattice of the iMeH.

When the microwaves are not being applied into the reactor, the gaseoushydrogen (H₂) flows into the reactor to replenish the hydrogen consumedby the monatomic (H•) hydrogenation reactions. When the gaseous hydrogencontacts the surface of the iMeH, it is dissociated into monatomichydrogen (H•) by the fundamental nature of the iMeH and is absorbed intothe interstitial structure of the iMeH. There is a useful, but reduced,catalytic effect when using iMeH without the benefit of microwaves. Inthe case without microwaves, an equilibrium exchange is reached wherebythe rate of gaseous hydrogen (H₂) into the iMeH is in balance with therate of monatomic hydrogen (H•) reacted into the feedstock. However theequilibrium rate of monatomic hydrogen (H•) reacted into the feedstockis typically lower without microwaves. Using the hydrogenation ofnaphthalene as an example, microwaves tripled the production of decalinand increased hydrogen uptake by 62% to 6.5wt %, as shown in Tables 4and 7, Example 6.

EXAMPLE 6 Quantitative Hydrogenation Test Results for Naphthalene

A sequence of tests was conducted on naphthalene (C₁₀H₈) as a modelcompound to demonstrate the hydrogenation capability of the iMeHcatalysts and the effect of microwave enhancement of the hydrogenationreactions catalyzed by iMeH. Shown in this example are tests conductedunder identical temperature and pressure (200° C. and 50 psi H₂) and thesame liquid hourly space velocity (LHSV) setting of 0.5. The microwavefrequency was 2.45 GHz.

The feed naphthalene solution was prepared with n-dodecane (n-C₁₂H₂₆) assolvent, and n-nonane (n-C₉H₂₀) as an internal standard. Majorhydrogenation products include tetralin (C₁₀H₁₂) and cis- andtrans-decalin (C₁₀H₁₈). The formation of tetralin requires the additionof four hydrogen atoms per molecule, while the formation of decalinneeds the addition of 10 hydrogen atoms. Decalin is the fully-saturatedreaction product for the hydrogenation of naphthalene. The yield oftetralin and decalin is a measure of the extent of naphthalenehydrogenation, as shown through the following reactions:C₁₀H₈+2H₂→C₁₀H₁₂ (tetralin)C₁₀H₈+5H₂→C₁₀H₁₈ (cis- and trans-decalin)

After a test, the product gas phase and liquid phase were analyzed withgas chromatographs (GC) to determine their chemical makeup. The GCresults allowed for quantitative determination of the concentration ofnaphthalene remaining in the product and the amounts of tetralin and cisand trans decalin produced. A mass balance was performed for each test.The change in hydrogen content was calculated by subtracting thehydrogen in feed from the hydrogen in product.

The following test results show that the iMeH catalyst has a largehydrogenation capacity, even at significantly lower pressure (200° C.,50 psi). Such capacity is significantly enhanced with the application ofmicrowave energy.

Test results provide evidence of the advantages of using interstitialmetal hydrides (iMeH) with and without microwave energy. Data for threedistinct classes of iMeH catalysts are presented, Cat 100, Cat 200, andCat 300. The iMeH component is mixed with a commercial ultra-stabilizedY (USY) zeolite powder with a silica to alumina ratio of 80. The USYpowder was tested as is or chemically coated with 1 wt % palladium (Pd).All catalysts were tested in pellet form.

The combinations of support and iMeH catalyst combination are notoptimized, and do not limit the use of iMeH with other supports forother hydrogenation examples (ZSM-5, ZrO₂, silica, alumina).

Other catalytic materials tested included a commercial H-Oil catalystand hydride materials prepared by conventional methods.

The iMeH powder was mixed with Pd coated or uncoated USY powder at twocomposition levels (30 wt %, 50 wt %).

The test results in tabular form displayed by the product hydrogenuptake and the weight percent of decalin produced, nonnalized to thetotal conversion of naphthalene feed.

Three tests are presented in Table 3. They compare three catalystcompositions used for naphthalene hydrogenation tests. These tests wereprocessed using conventional heat at the process conditions of 200° C.,50 psig, 0.5 LHSV. The first catalyst, 100% USY is a zeolite support isshown to be ineffective at hydrogenating naphthalene at these processconditions. The second catalyst was made by the addition chemicallydispersed palladium, 1 wt % Pd, to the USY support, by techniques knownto those skilled in the art. Palladium is known a hydrogenationcatalyst, but this naphthalene hydrogenation reaction is generallyperformed at pressures exceeding 1000 psi. This catalyst allowed forproduction of tetralin yielding a hydrogen uptake of 1.6%. The lastcatalyst was made by mixing 30 wt % of iMeH Cat 100 power together withUSY powder. This catalyst resulted in a hydrogen uptake of 1.9%demonstrating that the iMeH Cat 100 is an effective hydrogenationsubstitute for paladium.

Naphthalene Hydrogenation Tests Comparing Catalyst with iMeH Cat 100Processed with Conventional or Microwave Energy

Table 4 presents the test results of catalyst containing iMeH Cat 100 attwo concentrations, 30 wt % and 50 wt %. These tests were processedusing either conventional heat or microwave energy at the processconditions of 200° C., 50 psig, 0.5 LHSV. The USY powder was coated with1 wt % palladium and mixed together with iMeH Cat 100 powder. Allcatalyst combination provided for higher hydrogen uptake and theproduction of the more fully saturated decalin. Conclusions drawn fromthis data include:

-   -   Hydrogen uptake is enhanced by combining the Pd coated USY with        Cat 100    -   Hydrogen uptake increases with increased Cat 100 content    -   Hydrogen uptake is enhanced with microwaves

Table 5 presents the test results of catalyst containing iMeH Cat 200 attwo concentrations, 30 wt % and 50 wt %, and iMeH Cat 300 at the 50 wt %concentration. These tests were processed using either conventional heator microwave energy at the process conditions of 200° C., 50 psig, 0.5LHSV. The USY powder was coated with 1 wt % palladium and mixed togetherwith iMeH powder. Conclusions drawn from this data include:

-   -   Cat 100 hydrogenates naphthalene better than Cat 200    -   Hydrogen uptake/decalin production, for Cat 200, is        significantly enhanced with microwaves    -   Hydrogen uptake increases slightly with increased Cat 200        content    -   Cat 300 hydrogenates better than Cat 200 but less than Cat 100

The hydrogenation performance of each iMeH material can be explained bythe level of monatomic hydrogen produced at the operating conditions of200° C. and 50 psig. It should be noted that multiple test runs, underidentical conditions, indicate a standard deviation of less than 3% ofvalue for the increase in hydrogen content and for decalin production.Test results for the present invention now allow for a method todetermine the proper pressure and temperature to maximizehydroprocessing given the input feedstock and the desired product.

Table 6 compares the performance of prior art or commercial catalysts.These tests were processed using either conventional heat or microwaveenergy at the process conditions of 200° C., 50 psig, 0.5 LHSV.

Commercial H-Oil catalyst was processed using microwave energy, as it iswell known that it does not work well at low pressures. The lack ofhydrogenation of current best practice catalysts demonstrates theeffectiveness of iMeH catalysts of the present invention.

The second catalyst was a metal hydride prepared by conventional methodsand tested using conventional heat. The lack of hydrogenationdemonstrates that it does not function as an iMeH catalyst of thepresent invention.

Table 7 compares iMeH Cat 100 at two microwave energy power levels andin a partially oxidized state. These tests were processed usingmicrowave energy at the process conditions of 200° C., 50 psig, 0.5LHSV. All previous tests were conducted at a set microwave power level 1estimated to be one watt/cm³. A second microwave power level, powerlevel 2, was selected for comparison and is estimated to be 1.9watts/cm³. For both microwave power levels, the microwave energyprovides both the preheat energy and the reaction enhancement energy.

The test results show that significant increase in hydrogen uptake, 47%increase, and an increase in decalin production, 128%, was realized byadjusting the microwave to power level 2. It is thought that the highermicrowave power setting provided more microwave energy to the reactionas the bulk temperatures were held to the same levels. The thirdcatalyst, of the same composition, was prepared without the precautionstaken according to the present invention to minimize the formation of anoxide layer on the iMeH. The resulting reduction of 58% hydrogen uptakeand reduction of 99.8% of decalin production demonstrates theeffectiveness of iMeH catalysts of the present invention.

EXAMPLE 7

Benzothiophene Ring Opening

Tests were done with the model compound benzothiophene to showdesulfurization via ring opening. Benzothiophene is an aromatic,heterocyclic sulfur compound, with a side benzene ring, commonly foundin petroleum (C₈H₆S). Tests were performed using a benzothiophenesolution prepared with dodecane as a solvent and nonane as an internalstandard.

The benzothiophene solution was processed using an iMeH Cat 300, 50%Cat300-50% USY (1% Pd), with microwave energy at 2.45 GHz, power level 2at the processing conditions of 200° C., 50 psig, and 0.5 LHSV. 93% ofbenzothiophene was converted, and H₂S gas was detected, demonstrating ahydrodesulfurization process via carbon-sulfur bond cleavage and ringopening.

EXAMPLE 8

Quantitative Hydrogenation Test Results for Commercial Test Feeds

The following tests were performed with commercial test feeds. Thesetests include light gas oil (LGO), coker-kero oil, and heavy vacuum gasoil (HVGO).

The present invention works at much lower pressures than existinghydroprocessing reactions. This provides additional flexibility inselecting process variables. For example, for any given feedstock, theprocess temperature and pressure determine the fraction of organiccompounds in the vapor phase and the fraction in the liquid phase.Depending on the hydroprocessing reaction, controlling the vapor toliquid fraction ratio can improve the process efficiency. This is trueat temperatures below 550° C. at pressures below 600 psig and especiallyfor pressures below 300 psig.

The following test results provide one skilled in the art examples todetermine the proper catalyst composition and reaction conditions (i.e.temperature, pressure, LHSV, microwave energy level) to maximizehydroprocessing for a given feedstock and desired product.

Light Gas Oil Hydrogenation Tests

Light Gas Oil (LGO) is petroleum fraction containing a complex mixtureof hydrocarbons with a boiling point range from 140 to 450° C. at oneatmosphere. 90% of the hydrocarbon compounds boil between 160-370° C. atambient pressure. The level of aromatics in the LGO is estimated to beabout 30 wt %. The feed was placed in a batch microwave reactor inquantities and time to treat the feed at 0.5 LHSV. An HCNS analyzer wasused to measure the feed and product hydrogen to carbon (H/C) molarratio. The higher the H/C ratio, the more hydrogen in the product. Testresults are presented to show the increase in hydrogen content (wt %)added to the product.

LGO was processed using an iMeH Cat 300 catalyst, 50% Cat 300-50% USY(1% Pd). Two tests were performed using microwave energy at 2.45 GHz,power level 2, at two different operating pressures, 50 psig or 150psig, at the same test conditions of 200° C., and 0.5 LHSV. At 50 psig,the LGO was hydrogenated increasing the hydrogen content in the productby 0.2 wt %. At 150 psig, the amount of hydrogenation increased by afactor of two to 0.4 wt %.

Coker-Kero Hydrogenation Tests

Table 8 shows test results with coker-kero feed. Coker-kero feed is alow-value product fraction from the coking process. It contains acomplex mixture of organic compounds with a boiling point range from 160to 400° C. 90% of the organic compounds boil between 200-360° C. It hasa high-level of aromatic content, and a sulfur content of over 3.5 wt %.

Table 9 presents the coker-kero hydrogenation test results for an iMeHCat 300, 50% Cat 300—50% USY (1% Pd). Three tests were performed usingmicrowave energy at 2.45 GHz, power level 2, and 0.5 LHSV. The testscompare the effects of increasing either the operating temperature oroperating pressure from the process conditions of 200° C., 50 psig, 0.5LHSV.

The test results from Table 8 show that the iMeH Cat 300 catalyst wasable to hydrogenate and to hydrodesulfurize the coker-kero. The level ofhydrogenation doubled and the level of desulfurization increased by 8fold when the operating pressure was changed from 50 psig to 150 psig.This same increase in hydrogenation and desulfurization was observedwhen the operating temperature was increased to 250° C. For this examplea process pressure increase from 50 to 150 psig at 200° C. wasapproximately equal in hydrogenation performance to a change in processtemperature from 200 to 250° C. at 50 psig.

These results are significant because this sulfur reduction, performedat low pressure, is due to hydrogenation of the sulfur-bearing compoundswithout the use of standard desulfurization catalysts such as Ni/Mo andCo/Mo. The palladium metal component of this catalyst is not generallyused in industry for desulfurization because it is readily poisoned bysulfur.

Additional tests were carried out with a catalyst using 50% iMeH Cat 300with a 50-50 mixture of USY(1% Pd) and a sulfided Ni/Mo supportedalumina. The coker-kero was processed with a combination of conventionalpreheat and microwave energy. The process conditions were feed preheatto 400° C., reaction temperature 405° C., 150 psig, 0.5 LHSV. Theaverage microwave power density at 2.45 GHz was estimated to be 0.12watts/cm³.

The analysis of the feed and product showed an increase in producthydrogen content of 0.51 wt % and the level of hydrodesulfurization was57.3% (i.e. sulfur content reduced from 3.61 wt % sulfur to 1.54 wt %sulfur). It is believed the higher level of desulferization isattributable to the addition of the sulfided Ni/Mo alumina to catalystpellet. Table #9 shows the improvement of other physical propertiesincluding a 65% increase in the cetane index.

Heavy Vacuum Gas Oil Hydrogenation Tests

Heavy vacuum gas oil is obtained from the residue of atmosphericdistillation using reduced pressures (25-100 mm Hg) to avoid thermalcracking. The boiling range is approximately 260 to 600° C. at oneatmosphere pressure. The density is approximately 0.97 g/ml. Thearomatic content is greater than 50% and the sulfur content is about 3.5wt %.

Tests were carried out with a catalyst using 50% iMeH Cat 300 with a50-50 mixture of USY(1% Pd) and a sulfided Ni/Mo supported on alumina.The HVGO feedstock was processed with a combination of conventionalpreheat and microwave energy. The process conditions were feed preheatto 400° C., reaction temperature 405° C., 150 psig, 0.5 LHSV. Theaverage microwave power density at 2.45 GHz was estimated to be 0.12watts/cm³.

The analysis of the feed and product showed a slight increase in producthydrogen content of 0.08 wt % but the level of hydrodesulfurization was68.8%. It is believed the higher level of desulfurization isattributable to the addition of the sulfided Ni/Mo alumina to catalystpellet. Also, during the test ammonia was detected in the gas phaseproviding evidence of hydrodenitrogenation. Table #10 shows theimprovement of other physical properties including a reduction inviscosity from 174 cSt to less than 7 cSt and a 55% increase in the APIgravity. TABLE 1 Percent iMeH Hydrogen Released Cat 100 Cat 300 Heatedto 200° C. Heated to 350° C.  @ 0 psig 100%  100%   @ 50 psig 52% 48% @100 psig 25% 23%

TABLE 2 Properties of Pitch Residuum Before and After MicrowaveProcessing Microwave ASTM Pitch Processed SAMPLE Test Residuum PitchSpecific Gravity @ 60° F. D1298 1.001 0.998 Sulfur, Wt % D129 4.93 4.57Pour Point, ° F. D97 95 30 Kinematic Viscosity, D445 413 @ 100° C. 7.1 @50° C. cSt @ 50° C. or 100° C. Simulated Distillation D2887 Naphtha(IBP-160° C.) 0.0% 0.0% vol % Kerosene (160-260° C.) 2.0% 20.0% vol %Diesel (260-370° C.) 70.0% 75.0% vol % HVGO (370-514° C.) vol % 28.0%5.0%

TABLE 3 Naphthalene Hydrogenation Tests with Conventional Heat ComparingCatalyst with and without Pd to catalyst with iMeH Cat 100 TestConditions: 200° C., 50 psig, 0.5 LHSV Increase in Catalyst HydrogenDecalin Material Process Energy Content (wt %) % Produced 100% USYConventional 0.0% 0.0% 100% USY (1% Pd) Conventional 1.6% 0.0% 30% Cat100-70% Conventional 1.9% 0.0% USY (No Pd)

TABLE 4 Naphthalene Hydrogenation Tests Comparing Catalyst with iMeH Cat100 Processed with Conventional Heat or Microwave Energy TestConditions: 200° C., 50 psig, 0.5 LHSV Increase in Catalyst HydrogenDecalin Material Process Energy Content (wt %) % Produced 30% Cat100-70% Conventional 2.9% 1.4% USY (1% Pd) 30% Cat 100-70% Microwave3.2% 9.9% USY (1% Pd) 50% Cat 100-50% Microwave 4.5% 40.9% USY (1% Pd)

TABLE 5 Naphthalene Hydrogenation Tests Processed with Conventional Heator Microwave Energy for Catalysts Containing iMeH Cat 200 or iMeH Cat300 Test Conditions: 200° C., 50 psig, 0.5 LHSV Increase in CatalystHydrogen Decalin Material Process Energy Content (wt %) % Produced 30%Cat 200-70% Conventional 2.6% 0.0% USY (1% Pd) 30% Cat 200-70% Microwave3.4% 14.3% USY (1% Pd) 50% Cat 200-50% Microwave 3.5% 17.8% USY (1% Pd)50% Cat 300-50% Microwave 3.8% 24.0% USY (1% Pd)

TABLE 6 Naphthalene Hydrogenation Tests for Comparison to Prior ArtCatalysts and Metal Hydride Processed with Conventional Heat orMicrowave Energy Test Conditions: 200° C., 50 psig, 0.5 LHSV Increase inCatalyst Hydrogen Decalin Material Process Energy Content (wt %) %Produced H-Oil Catalyst Microwave 0.1% 0.0% Conventional Conventional0.1% 0.0% Metal Hydride

TABLE 7 Naphthalene Hydrogenation Tests Comparing iMeH Cat 100 at TwoMicrowave Energy Power Levels and in a Partially Oxidized State TestConditions: 200° C., 50 psig, 0.5 LHSV Increase in Catalyst HydrogenDecalin Material Process Energy Content (wt %) % Produced 50% Cat100-50% Microwave 4.5% 40.9% USY (1% Pd) Power Level 1 50% Cat 100-50%Microwave 6.5% 93.4% USY (1% Pd) Power Level 2 50% Oxidized Microwave2.7% 0.2% Cat 100-50% Power Level 2 USY(1% Pd)

TABLE 8 Coker-Kero Hydrogenation Test Results Processed with MicrowaveEnergy for iMeH Cat 300 Catalyst, 50% Cat300-50% USY(1% Pd), at ThreeCombinations of Operating Temperatures and Pressures Test Condition: 0.5LHSV Process Process Increase in Temperature Pressure Hydrogen % Sulfur(° C.) (psig) Content (wt %) Reduction 200 50 0.24% 5.5% 200 150 0.42%42.4% 250 50 0.44% 44.6%

TABLE 9 Physical Properties of Coker-Kero Before and After ProcessingCatalyst: 50% Cat300-25% USY(1% Pd)-25% sulfided Ni/Mo Alumina ProcessEnergy: Combination of Conventional Preheat and Microwave Energy TestConditions: 405° C., 150 psig, 0.5 LHSV Physical Coker-Kero ProcessedProperty Feed Product Cetane Index (ASTM D4737) 27 44 API Gravity 27 32Density @ 15° C. (gm/cc) 0.90 0.87 Viscosity @ 40° C. (cSt) 3.7 1.6

TABLE 10 Physical Properties of HVGO Before and After ProcessingCatalyst: 50% Cat300-25% USY(1% Pd)-25% sulfided Ni/Mo Alumina ProcessEnergy: Combination of Conventional Preheat and Microwave Energy TestConditions: 405° C., 150 psig, 0.5 LHSV Physical HVGO Processed PropertyFeed Product Cetane Index (ASTM 04737) −40 20 API Gravity 15 23 Density@ 15° C. (gm/cc) 0.97 0.91 Viscosity @ 40° C. (cSt) 174 6.8

1-15. (canceled)
 16. A catalyst comprising: a support; an RF ormicrowave energy absorber; and a catalytically active phase; wherein thecatalytically active phase stores and produces hydrogen in monatomicform.
 17. The catalyst of claim 16, wherein the catalytically activephase comprises an interstitial metal hydride.
 18. The catalyst of claim17, wherein the interstitial metal hydride has a reaction surface, andthe reaction surface is substantially free of an oxide layer.
 19. Thecatalyst of claim 16, wherein the support comprises at least one ofinorganic oxides, metals, carbon, and combinations thereof. 20-26.(canceled)